DE2650281A1 - LAUNDRY DETERGENT - Google Patents

Description

Our no. 20 759 Ka / La

The Procter & Gamble Company Cincinnati, Ohio, V ".St.A.

laundry detergent

Addition to main patent (patent application P 26 42 071-3)

The present invention relates to detergents and, more particularly, to detergents containing certain water-soluble ortho and contain pyrophosphates as builders.

The present invention provides detergents, the little or no formation of deposits on the drum surfaces and especially the heating elements from washing machines in which these detergents are used, cause and only slight deposition of insoluble matter cause inorganic material on the washed textiles.

As already explained in the main patent (P 26 42 071.3), The sodium and potassium ortho- and pyrophosphates can have more hardness ions (Ca, Mg) per P ^ O ^ unit in

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remove their constitution as sodium tripolyphosphate. The orthophosphates and pyrophosphates remove the hardness ions by precipitating these ions mainly as insoluble phosphates, while sodium tripolyphosphate keeps the hardness ions in solution as complex ions. This rainfall can occur in certain Cases cause undesirable effects on the fabrics, such as graying or roughness in the handle. According to the main patent this deficiency is largely overcome.

According to the main patent (P 26 42 071.3) this

substantial reduction in the concentration of inorganic deposited on the surfaces of the washing machine and fabrics Material provided by this

suspended
Material is kept in solution / and / or the surface of the tissue is modified in order to eliminate or minimize the tendency of the suspended inorganic material, which consists mainly of mixed calcium ortho and pyrophosphates, to bind to the tissue. This is indicated by low concentrations of selected crystallization modifying or colloid stabilizing materials which are believed to have both a peptizing effect in the wash solution

* also '^&

(bulk wash solution) as / a surface effect on the fabric cause that is less attractive for the bond with calcium phosphates and this more easily in subsequent washing operations gives, achieved.

The subject of the main patent (P 26 42 O7I.3) is

Therefore, a detergent, which is characterized by (A) 1 .to 70 wt -% of an organic surfactant.

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(B) 5 to 50 wt .- / l of a device made of sodium and / or Potassium orthophosphate and pyrophosphate, the weight ratio of orthophosphate to pyrophosphate in the range of 9: 2 up to 3: 7,

(C) OjI to 10 gen.% Of a scale inhibitor

(a) a particulate water-insoluble nucleation promoter,

(b) a polycarboxylate material

(1) Homopolymers with molecular weights from 500 to 250,000 with repeating units the general formula

wherein R. is hydrogen or the hydroxyl group and Rp represent hydrogen or the carboxyl group, their salts and preliminary products,

(2) Copolymers of maleic acid with ethylene, vinyl methyl ether or styrene, with molecular weights from 500 to 250,000, or their salts,

(3) Aryl maleic acid oligomers of the general formula

(CH-

CII) ₄ -H

COOK COOH

wherein R-, hydrogen or the methyl group and their salts, or ( ¹ O mixtures thereof, or
(c) Mixtures of (a) and (b).

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-X-

While according to the main patent (P 26 42 071.3)

Mixtures are provided according to which the deposit problem is substantially decreased, according to the present invention, an even more substantial decrease becomes of the deposit and even under unfavorable conditions, the mixtures according to the invention have a practical effect no deposition of undesirable insoluble phosphate salts.

The present invention relates to detergents which are characterized by

(a) from 1 to 70 wt -.% of an organic surfactant /

(b) from 5 to 50 wt -.% of a mixture of sodium pyrophosphate and / or potassium ortho- and wherein the weight ratio of orthophosphate to pyrophosphate in the range

is from 9: 2 to 3: 7, and

others

(c) from 0.1 to 10 wt -.% of a / the polymeric scale inhibitor as a copolymer of maleic acid with ethylene, styrene or Vinylmethylather, of units of the general formulas

or

wherein R each independently represents a hydrogen atom or an alkyl radical with 1 to 6 carbon atoms, R ₁ each independently represents a hydrogen atom, an OH radical, an ORg radical, where Rp denotes an alkyl radical with 1 to 3 carbon atoms, an OPh radical or a - OCH ₂ COOM-

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Remainder, M is a hydrogen atom or a cation and in and η Numbers mean that the molecular weight of the polymer is in the range of 500 to 100,000, and the ratio of m: n of 10: Ibis is 1:10.

A preferred range of orthophosphate to pyrophosphate ratios is from 7: 3 to 1: 1 and is particularly preferred becomes the range from 65:35 to 55: ^ 5 (parts by weight).

Any class of organic surfactants can be used, but it is preferred to use anionic, nonionic, or zwitterionic detergents, or mixtures of any of these detergents. The organic surfactant makes from 1 to 70 wt. of the mixture of ·, for solid granular detergents, the content of organic, surface-active agent is usually from 5 to 40% by weight , preferably from 10 to 30% by weight . The content of organic surface-active agent in liquid detergent mixtures is 30 to 70 %. Numerous examples of suitable surfactants are described in U.S. Patent 3,929,678, which is incorporated herein by reference.

Preferred surfactants and their combinations for use in the agents according to the invention are:

Anionic detergents, such as the C ₁₀ - to Cg and particularly about C alkyl benzene sulfonates, C .-- to CQ-alkyl sulfates and Polyäthoxyalkylsulfate, water-soluble soaps of ^C 10 ~ ^b ^ ^sc p2 ~ ^ ^{fatty acids and} mixtures thereof.

Nonionic detergents, especially the polyethoxy alcohols with 8 to 20 carbon atoms and 1 to 30, especially

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special 4 to 10 ethoxy groups and their mixtures. Valuable Iionionic mixtures are known from DT-OSn 2,448,532 and 2,511,667.

Particularly preferred nonionics are the more or less branched (usually with 2-methyl branching) primary Alkyl ethoxylates available under the trade names "Dobanol" and "Synperonie" and the secondary linear alkyl ethoxylates of the "Tergitol" series, especially those with 9 to 16 carbon atoms in the alkyl radical and up to 11, and especially 3 to 9 ethoxy radicals per molecule. Nonionics of this class are in BE-PSs 827 780, 827 781 and 824 848.

Zwitterionic detergents, especially the alkyldimethylammonium propane sulfonates and hydroxypropanesulfonates with alkyl radicals having 10 to 18, in particular about 15, carbon atoms .

Mixtures of the above anionic and nonionic detergents and the nonionic and zwitterionic detergents can also be used.

It has been found advantageous to use soaps as the anionic surfactant ingredient or part thereof. Preferred soaps are the sodium or potassium salts of C ₁₀ - to C __ - fatty acids ₅ such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, linolenic acid, stearic acid, arachidic acid and behenic acid, and usually the soaps of acid mixtures, which for example from coconut oil, palm oil, Kernel and / or tallow can be obtained, and from hydrogenated oils or fatty acids, such as "Hyfac" (trade name). The Ver-

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-S-

/ 10

Turning these soaps can bring one or more benefits. So the soaps can exert their usual cleaning effect. In addition, they can reduce the accumulation of residues on the washed laundry, they can have a textile-softening effect, they can reduce the deposition of dirt from the washing liquid on the clean laundry and, depending on the length of the fatty acid chain, they can increase, regulate or reduce the foaming of the detergent. The soap (or the soap residue, if a portion of long-chain soaps such as from Hyfac is used, e.g. as a foam suppressor) should be mainly short-chain, e.g. from the range C _1Q - to Cj, -, e.g. from coconut oil.

Particularly preferred organic detergent mixtures contain an anionic synthetic detergent such as a linear alkyl benzene sulfonate and a water soluble soap such as coconut soap in a weight ratio of 1:10 to 2: 1 and preferably about 1: 1. The mixture can optionally contain a foam-regulating amount of C-ig- ^b ^ ^s Cp_ soaps and / or tallow alcohol condensed with 7 to 25 mol of ethylene oxide, preferably a mixture which, based on the weight of the total agent, is 1 to 5 % each. (D contains soaps from Hyfac and (2) tallow alcohol condensed with 7 to 25 moles of ethylene oxide.

The main phosphate components are sodium and / or potassium ortho- and pyrophosphates. Sodium phosphates are preferred in solid agents, while the more soluble potassium salts are more suitable in liquids. It is important that both orthophosphates and pyrophosphates are present in the specified amounts. The average total orthophosphate and pyrophosphate content is preferably 10 to 35 and in particular 15 to 33% by weight . Is the content of pyrophosphate

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- 3 - Al

too low, the cleaning (dirt removal) ability deteriorates of the products.

The agents according to the invention can contain further inorganic or organic salts and compounds which are known to have detergent builder action, and also other salts or hydroxides which produce the desired alkalinity, as will be described in more detail below. The use of sodium tripolyphosphate or more strongly condensed phosphates such as vitreous metaphosphates does not impair the washing behavior of the agents. However, their use reduces the possible by the present means savings of phosphate, and preferably should not exceed 25 wt -.% Of one or the other, based on the total weight of phosphates, and not more than ¹ J wt -.% Glassy metaphosphates, based on the total agent.

Other inorganic salts with a builder effect and influence on the alkalinity of the agents are sodium or Potassium carbonates, borates, sulfates and silicates. Other inorganic builders are described in BE-PS 838 553. The latter can, if at all, be in quantities of 1 to 40 and preferably 5 to 25 weight / lb of the composition be.

Sodium silicate is preferably present in solid, granular or particulate compositions. It can have a molar ratio SiO ₂ : Na ₂ O of 1: 1 to 4: 1. The preferred molar ratios are 1.6: 1 to 3/2: 1, since this is where the most satisfactory spray-drying behavior and the best grain properties are achieved.

Examples of suitable organic detergent builders can also be found in BE-PS 838 553.

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The scale inhibitor of the present invention is a polycarboxylate material which either in the form of the salt of the Acid or in the form of the corresponding anhydride can be used. The materials are copolymers of an olefinic Monomers and a carboxylate monomer having repeating units of the general ones defined above Formulas. The general formulas do not signify any specific order of the monomer units. Normally the olefinic and carboxylic monomers are arranged randomly along the polymer chain.

Preferred olefinic monomers have at least one radical R, which is an alkyl radical with 1 to 6 carbon atoms, and a total number of carbon atoms of 5 to 10 in the monomer. Preferred olefins are propylene, Isobutylene, alkyl substituted isobutylenes and especially di-isobutylene. The preferred carboxylate monomer is Maleic acid, a maleate, or maleic anhydride. Preferred cations for the maleates are sodium, potassium or ammonium. Other substituted maleic acid derivatives can be used but are less readily available commercially.

Preferably, m and η in the general formulas are numbers such that the molecular weight of the polymer is in the range from about 500 to about 50,000, and preferably the ratio of m: n is about 1: 1 to 1: 2. A particularly preferred polymer is Epicryl APD (Albright and Wilson, Marchon Division) which is believed to be a copolymer of diisobutylene and sodium maleate. Other suitable copolymers are:
Propylene / maleic anhydride, isobutylene / sodium maleate,
2-methyl-but-2-ene / sodium maleate,

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2,3-dimethyl-but-2-en / potassium maleate,
Propylene / hydroxymaleic acid or its salts, di-isobutylene / hydroxymaleic acid or its salts and products derived from these hydroxymaleic acid polymers by etherification

Propylene / and di-isobutylene / 2-phenoxy-but-2-en-l, 4-dicarboxylic acid,

Propylene / and di-isobutylene / 2-0- (carboxymethyl) -but-2-en-1,4-dicarboxylic acid.

These copolymers can be prepared by methods well known in the art by copolymerizing the appropriate olefin and the salt or anhydride of the appropriate acid.

The polycarboxylate is preferably used in the form of its alkali metal, especially the sodium salt and the concentration, calculated as the sodium salt in the inventive mixtures is from 0.15 to 10 wt .- ^, preferably from 0.3 to 5 wt -.% And in particular from 0.5 to 3% by weight .

The scale inhibitor described above can be used alone in the mixture or can be used together with the

in the main patent (P 26 42 071.3) described

other scale inhibitors can be used. In particular Preferred mixtures according to the invention can also be used contain a particle-free / water-insoluble nucleation promoter, especially calcium pyrophosphate or magnesium silicate.

In the agents according to the invention, all customary Detergent components are present, taking into account the

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requirements according to the invention. These components include bleaching agents such as sodium perborate or percarbonate and organic peroxy compounds and chlorine bleaches, enzymes, activators and stabilizers for bleaches or enzymes, soil suspending agents or soil release agents such as sodium carboxymethyl cellulose or others Cellulose derivatives, foam regulating agents, such as fatty acid amides and ethanolamides or silicones, tarnishing inhibitors, organic solvents, hydrotropes (especially in liquid products) such as the lower alkylbenzenesulfonates, Dyes and perfumes.

The mixture can be spray-dried to provide a granular mixture or dried by other means. Usually, non-stick, free flowing grains are obtained at a moisture content of from about 3 to about 10 %. Lower moisture contents, as described in BE-PS 838 553, can also be used. Occasionally, higher moisture contents are recommended. Epsom salts or the like can be mixed into the granular mixture described above; other components,

dry

such as bleach and enzymes that detergents are usually mixed with be added.

In the production of the agents according to the invention do not have to all phosphates are spray dried, rather some or all of the phosphate can be dry with the spray dried (or otherwise dried) grains containing the remaining ingredients of the agent mixed will.

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The following examples serve to illustrate the present invention.

Examples

The following mixtures according to the invention were obtained by spray drying a slurry (crutcher mix) that contains all components except perborate and magnesium sulfate, which make the spray

removed, dried granules were mixed dry, / produced:

1 Examples 3 4th 5 mixture 8.0 2
Cf 8.0 8.0 8.0 Sodium linear dodecyl
benzenesulfonate 10.0 la
8.0 - - - Sebum soap - - - - 10.0 Coconut soap 6.1
(2.0) 10.0 6.1
(2.0) 6.1
(2.0) 6.1
(2.0) Sodium silicate
(Ratio SiO ₂ : Na ₂ 0) 12.0 6.1
(2.0) 22.0 18.5 8.5 Sodium sulfate 1.7
3.5 12.0 1.7
3.5 1.7
3.5 1.7
3.5 Day-E ₁₁
Fatty acid (G-jooq) 7.7 1.7
3.5 7.7 8.8 8.8 Components in smaller
Quantities and moisture 10.0 9.7 - 10.0 10.0 10.0 Trx sodium orthophosphate 6.0 10.0 6.0 6.0 6.0 Tetrasodium pyrophosphate 2.0 6.0 2.0 - - Magnesium sulfate 32.0 - 32.0 32.0 32.0 Sodium perborate 1.0 32.0 1.0 1.5 1.5 Empicryl APDB 90 100.0 1.0 100.0 100.0 100.0 100.0

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With these mixtures, a cleaning was as good as with a fully formulated with tripolyphosphate as a builder Mixture achieved. The build-up on the washed fabrics was very little and was even less in use of the soap-containing mixtures than when using the non-soap mixtures.

The same results were obtained when the Empicryl was not used in the slurry but was mixed dry with the spray-dried granules. The same results were also obtained when the anhydride corresponding to the Empicryl is used. It is believed that Empicryl APDB 90 comprises at least 76% of a copolymer of diisobutylene and sodium maleate and has a molecular weight of about 5,000.

The following examples represent examples of further mixtures according to the invention:

Examples mixture 6789 10

Sodium dodecyl benzene

sulfonate 14.0-8.0-20.0 8.0

Condensation product
of 3 moles of ethylene oxide
with 1 mole of C fatty alcohol ¹ ^ 1.0 - 3.0 - - 3.0

Condensation product
of 7 moles of ethylene oxide
with 1 mole of a C * u ~
C ₁ alcohol 3.5 15.0 2.0 12.0 3.0 3.0 Stearic acid 15.0 - 14.0 - 24.0 10.0 Sodium orthophosphate 15.0 10.0 28.6 10.0 8.0 6.0 Sodium pyrophosphate 6.1 6.0 6.1 6.0 10.0 10.0 Sodium silicate 6.1 10.0

(SiO ₉ : Na _o 0 ratio
2.0) ^{2 2}

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mixture

Magnesium silicate (SiO ₀ : MgO ratio 3.2) ²

Sodium Sulphate Sodium Perborate Copolymer I Gopolymer II Empicryl APDB 90

Moisture and components in smaller quantities

0 2650281 Examples 7th 8th 9 10 11 0 * % Ji % % 6th 0 3.0 - 3.0 - 3.0 % 20.0 _ 25.0 _ 22.0 - 30.0 30.0 25.0 28.0 28.0 10, - - - 1.5 - 30, - 2.5 - - 1.5 ι, 1.5 - 1.5 - - - -on 100 -

Copolymer I represents a copolymer of propylene and Maleic anhydride.

Copolymer II is a copolymer of 2,3-methyl-but-2-ene and potassium maleate.

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Claims (11)

Patent claims: (a) from 1 to 70 wt -.% of an organic surfactant, (b) from 5 to 50 wt .- # of a mixture of sodium and / or potassium orthophosphate and pyrophosphate, the weight ratio of orthophosphate to pyrophosphate ranges from 9: 2 to 3: 7, and (c) from 0.1 to 10 wt -.% represents a polymeric scale inhibitor which is not a copolymer of maleic acid with ethylene, styrene and Vinylmethylather or units of the general formula C - C f- or COOM C00] \ wherein R is independently a hydrogen atom or an alkyl radical having 1 to 6 carbon atoms, PL is each independently a hydrogen atom, an -OH radical, an -ORp radical, where Rp is an alkyl radical having 1 to 3 carbon atoms, an -OPh radical or a -0CH ₂ C00M radical, M a hydrogen atom or a cation and m and η denote numbers, so that the molecular weight of the polymer is in the range from 500 to 100,000, and the ratio of m: n from 10: 1 to 1: 10 is included. 809812/055 2 2. Detergent according to claim 1, characterized in that at least one of the radicals R is an alkyl radical having 1 to 6 carbon atoms, the 4 radicals R contain a total of 1 to 8 carbon atoms, R ₁ is a hydrogen atom and the molecular weight of the copolymer is in the range of 500 to 50,000. 3. Detergent according to claim 2, characterized in that it is copolymers of isopropylene as a deposit inhibitor and sodium maleatej isobutylene and sodium maleate or Contains diisobutylene and sodium maleate and the molecular weight of the polymer ranges from 1,000 to 10,000 lies. 4. Detergent according to one of claims 1 to 3, characterized in that that the surface-active agent is an anionic or non-ionic detergent or a mixture is the same. 5. Detergent according to one of Claims 1 to 4 in granular form, characterized in that it contains from 5 to 30 % of the organic surface-active agent. 6. Detergent according to one of claims 1 to 5 »characterized in that that the surfactant is one or more water-soluble soaps of fatty acids with 10 to Comprises 22 carbon atoms. 7. Detergent according to claim 6, characterized in that the water-soluble soap has 10 to 14 carbon atoms having. 809812/0552 8. Detergent according to one of claims 1 to 7, characterized in that the surface-active agent is a
anionic synthetic detergent and a water soluble soap in a weight ratio of 1:10 to 2: 1. 9. Detergent according to one of claims 1 to 8, characterized in that it is from 15 to 33 % of the mixture
which contains orthophosphates and pyrophosphates. 10. Detergent according to one of claims 1 to 9, characterized characterized in that the weight ratio of orthophosphate to pyrophosphate in the range from 7: 3 to 1: 1. 11. Detergent according to claim 10, characterized in that the weight ratio is in the range from 65:35 to 55: ^ 5 lies. For: The Procter & Gamble Company
Cincinnati, Ohio, V.St.A. • .H. \ Chr.] Dr.H.pir.Beil
Lawyer 809812/0552